Process for refining dammar resins



Patented Sept. 4, 1945 1 UNITED STATES PATENT orncs 2,384,138 Q PROCESS FOR REFINING RESINS Norman C. Schultze, Baltimore; Md., assignor, by

mesne assignments, to U. S. Industrial Chemicals, Inc., a corporation of Delaware .No Drawing. Application May 29, 1942,

Serial No. 445,039

7 Claims. (01. 260 10 HI comprises the insoluble resins typified by This invention relates tothe processing of natural resins which are soluble inorganic solvents of the hydrocarbontype.

Natural resins have ,been further classified according to the following:

Class I. Dammar resins A-Batavia B'Singapore Class II. East India resins (resins related to the I prefer to group thenatural resins into three major groups.

Group I. Those which can be divided into alcohol soluble and alcohol insoluble constituents:

A-Batavia BSingapore C-Batu- D-B1ack I E-Pale East India Singapore FPale East India Macassar Group III Those which are alcohol soluble:

A-Manila B-Kauri C-Accroides DMastic E-Sandarac I Group III. The insoluble type:

A-Congo Group I includes the dammar resins and'related resins which can properly be classed as dammars. These resins can be separated into two major constituents; namely, alcohol soluble portions, or alpha-resenes, and the alcohol insoluble portions, or beta-resenes. Group II represents the alcohol soluble resins, and Group Congo resins.

The natural resins have the disadvantage of containing dirt, insoluble matterand gelatinous, non-resinousparticles. In order to remove the dirt and. gelatinous matter, it is necessary for the consumer to process the resins. This involves added expenditures in time, tie-up of equipment, loss of solvent and resin. 7

Acharacteristic of the resins of Group I, in which are dammars, is that members of this group of crude resins are not completely compatible with common lacquer materials. To make them usable, they are generally treated by a process known as dewaxing. An example of such a dewaxing procedure is as follows: Dissolve pounds of resin in 40 pounds of tol uene and 40 pounds of ethyl acetate. After solution .is complete, 40 pounds of ethyl alcohol are added, the mixture is thoroughly agitated, and the wax," or beta-resene, is allowed to settle out. The liquid and the precipitate are then subjected to a filtration or a clarifying operation which removes the precipitated wax togetherwith other impurities such as bark, dirt, and sand. r

Such methodsof preparing dewaxed. resins for commercial use have disadvantages. of the disadvantages are that the dewaxed resin solutions lack flexibility in formulation of given lacquers and varnishes because of thevariable concentrations of the. solvents present; that the solutions ,are otherwise variable in their con tents; that they are likely to be darker thandesirable because of solution of color bodies: contained -'in the extraneous material- (bark,v dirt and the .like) bythe action of-the fdewaxing solvent; and that the wax, or beta-.resene, andvarying quantities of the entrained solvent'mix ture are, usually lost bythe users of this group of resins. H

An object of .thisinvention is to produce purified, natural resins-of the Group I type in a solid form, substantially, freeof solvents and extraneous materials. The use of these purified solid 'resins will overcome the disadvantages ofresin solutions obtained by treating the natural resins of that type by. the familiar dewaxing or extraction. methods. The invention is not limited to the preparation of solid resins, however. It is also applicabletothe production of improved alpha-resene solutions of resins of .Group I, or of run? resins of thatv group. These solutions can be used directly to.better advantage than the customary resin solutions.

Some

A further object of this invention is to produce a commercial grade of beta-resene, or wax, from resins comprising Group I, free of dirt and other extraneous matter, and also substantially resin; then the extraneous .rnaterial, is removed 7 before any further processing which would tend to leach out color bodies andthus impartcolor to Y Other features, objects and advantages Will-sippear from the descriptions thatfollow, itbeing understood, however, that the detailed deseripf tions are given by Way of illustration and not by way of limitation, since various changes may be made in procedure without departing from the scope and spirit of the invention. v I I H By way of illustration, the treatmentiof a'grade of resin commonly known to the trade as damimar Singapore seeds, typifying resinsof Group I, will be'described, but it will be understood that the invention is applicable to' the processing oi other grades of Singapore dammars, as well as other resins of this group I It may be further explained that when the natural resins are, dissolved or dispersed in a solvent, the resulting dispersion is not readily freed of extraneous matter by filtration because of plugging f the pores of the filter medium by a gelatinous materialr As a consequence, settling has generally been resorted to by theusers of the dispersions of natural resins. Much time is lost through tie-upin storage, however, and the residual materials contain a large percentage of sol'-; ventand resin. In addition, certain cold cuts contain a'eloud that settles very slowly ajnd finally, a large number o'fstorage tanks is re quired forjcapacity. a r ,1 e

vi l it ad W nb i'w t t E 13? inous substances referredto could not be removed by centrifuging. I have found, however, that after the resins havebeen dispersed in the pri mary solvent heretofore mentioned, gelatinous bodies, together with other extraneous materials.dirt, et c.-'can' bereadily separated from the resin solution or dispersion by treatment in the supercentrifuge. Before this treatment, it is advantageous to'remove relativelylarge particles of foreignmaterial, either by coarse filtration or by ordinary centrifuging. The term supercentrifuging 'used' herein means an operation in which centrifugal force is upwards to that of 13,200 times that of gravity In ordinary cerif trifiging, the centrifugal force seldom exceeds 1,000 times that of gravity. V x

As a further novel practice in a process for the purific tioapf natural es I have i b ste be recovered from the precipitation mist e by decantation, filtration, or the like, and then dried,

To further illustrate this inventioh, n' m ychoose such a solvent as'tolune to disperse the ibeing economic considerations.

large particles of extraneous matter may be accrude resins of Group I. The primary solvent may comprise one or more of the following solvents, or mixtures of them: benzene, toluene, xylenes, volatile petroleum hydrocarbon fractions, solvent naphthas, and the like. I prefer that the resin be dispersed by adding it to the solvent or solvents withag itation at a solid concentration approximating 46%". Lower 6r higher concentrations may be used, the limiting factor Removal of the yprocessis then'supercentrifuged for the removal ol -substantially all the fine solids and gelatinous material present, In certain instances it may be helpful to heat the coarse filtered resin solution or dispersion before supercentrifuging. This supercentrifuge efiluent may be concentrated at process, is of value in" the trade.

either atmospheric pressure, or at a reduced pressure, betore dewaxing'. H 7

The clarified resin solution is dewaxed by the addition of an organic non-solvent for the wax, such as ethyl alcohol, or thetlike. Othenn ldnohydricalcohols of 1-4 carbon atoms and 3-4 car-- bon atom ketones or mixtursmay be'use'd instead of, or with, ethyl alcohol. If the de'waxe'd resin is to be obtained in solid form, it is preferable that the dewaxin'g liquid bewater miscible. If the refined resin is to be marketed as a solution, the dewaxing agent may be water immiscible.

Removal of the wax may be accomplished by filtration, decantati'on; etc. The wax may then be washed With' a water-miscible non-solvent for the wax, or with mixtures of water miscible non-solvents for the wax, to remove occluded alcohol-soluble resin. The solid wax is then subjected to any of the known methods of drying. It is of significance that the wax from the usual dewaxing procedures is lost to' the users of resins of Group I. This wax, when free of extraneous matter, as obtained from the above It is a White amorphous material of low acid numbers and high melting points and imparts false body and a flat finish to varnishes.

The dewaxed resin solution or dispersion ,containing toluene and alcohol is subjected to a concentrated alcoholic solution for directuse.

Or, the distillation may be carriedofit irr such a manner as to leave the resin disper d in toluene. I may in certain instances disperse the clarified resin a variety'of solvents stated concentrations and remove the primary solvent and the 'de'waxing solvent at atmospherie or diminished pressures. It is highly desirable; however, to recover the resin in solid form, virtually free of solvent. I

To this end the solutions or dispersions of resins of Group I, dispersed in a wa ter miscible solvent, are fed into an amount of water of such quantity as to produce a non-tacky precipitate of the resin. It may be desirable to increase the .concentration of the water miscible solvent or solvents in the precipitating bath, inwhich event the temperature is lowered, te decrease the tendency of the precipitated resin to block or agglomerate. A V

Ifhe precipitate can be washed in this form, and may be subjected to such treatment as bleaching or neutralization. The bleaching agent, or the neutralizing'agent, or a mixture of the two, may be placed in the water miscible solvent or solvents containing-the resin, or the materials may be placed in the precipitating bath.

The precipitated resin is subjected to any oi the known methods of drying. The dried refined "dewaxed resins of Group I ofier advantages over the untreated natural resins in flexibility of formulation; The processed resin is'entirely soluble, as dirt and insoluble matter'have been removed. The processed resins are of uniform quality and good color. The processed resins, being free of dirt and wax, and in'a'solid form, can be used in plastics. When used with hot melts containing ethyl cellulose, the processed resins impart certain desirable "characteristics.

To illustrate further the process of refining natural'resins'of Group I asexplained above, the following specific example is given.

Twenty pounds or dammar resin, Singapore seeds grade, are dissolved in thirty pounds of toluene. The resultant solution or dispersion is coarse filtered through layers of cheese-cloth and is clarified by supercentriiuging. The supercentrifuged efliuent is then subjected to distillation at a reduced pressure to remove a quantity of toluene sufficient to concentrate the supercentrifuged eflluent to '75%-80% resin content. This distillation is carried out at 60 mm. pressure.

The resultant concentrated resin solution is poured into an amount of anhydrous alcohol equivalent to three times the weight of the resin, that is, into an amount of alcohol equal approximately to nine times the amount of toluene in the concentrated resin solution. The wax, or beta-resene, which is thereby precipitated, is removed by filtration or centrifuging and washed with alcohol to remove occluded alrohol-soluble resin. The beta-resene is then dried.

The filtrates from the dewaxing and washing steps are combined and subjected to distillation at a pressure of 350 mm. During this distillation the conditions are such that substantially all of the toluene is removed. The distillation is stopped at the point where a suitable concentration of resin is obtained.

The dewaxed resin is recovered from the alcoholic solution by precipitation in water, the amount of water used being sufficient to reduce the alcoholic content to 5% by volume. Precipitation of the alcoholic resin solution in water will require agitation, which should be continued for a period of time, to insure leaching of the alcohol from the precipitated resin.

The resin suspended in the alcohol-water mixture is filtered off and washed with water, and dried.

The above procedure will produce a wax and an alpha-resene, or dewaxed dammar, both of commercial value, free from extraneous matter. The products are free flowing, finely divided solids.

The following percentage figures illustrate the results obtained in refining a typical lot of Singapore seeds dammar according to the process outlined above:

-- 1: The process of refining natural resins con- -taining filterable andnon-filterable gelatinous impurities and wax which comprises dispersing there'siniin anorganicsolvent for the resin and "wax, subjecting the dispersion to a "coarse filtration to remove'filterable impurities, subjecting thefiltrate to supercentrifugal forces and thereby separating a sludge consisting of the gelatinous impurities and fine impurities not removed =by the coarse filtration,displacing' the solvent'in the dispersion with an organic solvent -for=the rsin'in which the wax is insoluble, separating the wax from the dispersion and conc'entrating the dispersion.

"*2. The'process of refining natural resins containing filterable and I non-filterable gelatinous impurities and wax which comprises dispers ing the resin in an organic solvent for the resin and "wax, subjecting the dispersion to a coarse filtration to remove filterable impurities, subjecting the filtrate to supercentrifugal forces and thereby separating a sludge consisting of the gelatinous impurities and fine impurities not removed by the coarse filtration, displacing the solvent in the dispersion with an organic solvent for the resin in which the wax" is insoluble, separating thefwax from the dispersion, concentrating the dispersion, and precipitating the resin therefrom.

3. The process of refining natural resins containing filterable and non-filterable gelatinous impurities and wax which comprises dispersing the resin in a hydrocarbon containing at least four and not more than ten carbon atoms, subjecting the dispersion to a coarse filtration to remove filterable impurities, subjecting the filtrate to supercentrifugal forces and thereby separating a sludge consisting of the gelatinous impurities and fine impurities not removed by the coarse filtration, displacing the solvent in the dispersion with an organic solvent for the resin in which the wax is insoluble, separating the wax from the dispersion and concentrating the dispersion.

4. The process of refining natural resins containing filterable and non-filterable gelatinous impurities and wax which comprises dispersing the resin in a hydrocarbon containing at least our and not more than ten carbon atoms, subjecting the dispersion to a coarse filtration to remove filterable impurities, subjecting the filtrate to supercentrifugal forces and thereby separating a sludge consisting of the gelatinous impurities and fine impurities not removed by the coarse filtration, displacing the solvent in the dispersion with an organic solvent for the resin in which the wax is insoluble, separating the "wax from the dispersion, concentrating the dispersion, and precipitating the resin therefrom.

5. The process of refining natural resins containing filterable and non-filterable gelatinous impurities and wax which comprises dispersing the resin in an amount of organic solvent for the resin and "wax such that the solid concentration of the dispersion is approximately 40%, subjecting the dispersion to a coarse filtration to remove filterable impurities, subjecting the filtrate to supercentrifugal forces and thereby separating a sludge consisting of the gelat- 2.1 inous impurities and fine impurities not removed n by the coarse filtratiorr,displacing :the solvent the dispersion with an organic-solvent for the which the sludge wasseparatedktq a; solidconcentration of approximately 75% to 80%,- displacing the sol-vent in the dispersion with an organic solvent for theresin-inwhich the wax is insei-u-ble, separating the-wax from the dispersiom-ami recovering the resinefrom the rern-ai-n-izig dispersion. 1

i L'TZV'I He process ofrefining natural resins containingfiiterableand non fi-lterab-le' gelatinous iinnurities and wax which comprises dispersring the. resin in Lan organic solvent for theresin and wa-x,=" subjecting the dispersion to a coarse filtration to remove filterable impurities subjecting the; filtrate tosupercen-trifuga-I forces and thereby separating a sludge consisting of the gelatinous 'i-mpurities and fine'impurities not re- IfiOVGd by the coarse filtration, concentrating the nitrat fromwhich-the sludge was separated to a-solidconcentration 0t approximately 15% to 80%; displacing' the solvent in the dispersion with an amount of, organic solventfor the resin,

in the wax is insoluble,- equal approximately to nine times the amoun-twof solvent in the-jdispersien, with resultant precipitation of if-Wax, separating; the waxf from the dispersion, and recovering the resin' from the remaining dispersion 1 j 1 NQRMAN G SCHULTZE. 

